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Heterometallic Molecular Complexes Act as Messenger Building Units to Encode Desired Metal-Atom Combinations to Multivariate Metal-Organic Frameworks.

ABSTRACT: A novel synthetic approach is described for the targeted preparation of multivariate metal-organic frameworks (MTV-MOFs) with specific combinations of metal elements. This methodology is based on the use of molecular complexes that already comprise desired metal-atom combinations, as building units for the MTV-MOF synthesis. These units are transformed into the MOF structural constituents through a ligand/linker exchange process that involves structural modifications while preserving their originally encoded atomic combination. Thus, through the use of heterometallic ring-shaped molecules combining gallium and nickel or cobalt, we have obtained MOFs with identical combinations of the metal elements, now incorporated in the rod-shaped secondary building unit, as confirmed with a combination of X-ray and electron diffraction, electron microscopy, and X-ray absorption spectroscopy techniques.

SUBMITTER: Lopez-Garcia C

PROVIDER: S-EPMC9479064 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

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Heterometallic Molecular Complexes Act as Messenger Building Units to Encode Desired Metal-Atom Combinations to Multivariate Metal-Organic Frameworks.

López-García Clara C Canossa Stefano S Hadermann Joke J Gorni Giulio G Oropeza Freddy E FE de la Peña O'Shea Víctor A VA Iglesias Marta M Angeles Monge M M Gutiérrez-Puebla Enrique E Gándara Felipe F

Journal of the American Chemical Society 20220812 36

A novel synthetic approach is described for the targeted preparation of multivariate metal-organic frameworks (MTV-MOFs) with specific combinations of metal elements. This methodology is based on the use of molecular complexes that already comprise desired metal-atom combinations, as building units for the MTV-MOF synthesis. These units are transformed into the MOF structural constituents through a ligand/linker exchange process that involves structural modifications while preserving their origi ...[more]

PMID: 35960870

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Project description:Understanding the fundamental properties governing metal-metal interactions is crucial to understanding the electronic structure and thereby applications of multimetallic systems in catalysis, material science, and magnetism. One such property that is relatively underexplored within multimetallic systems is metal-metal bond polarity, parameterized by the electronegativities (χ) of the metal atoms involved in the bond. In heterobimetallic systems, metal-metal bond polarity is a function of the donor-acceptor (Δχ) interactions of the two bonded metal atoms, with electropositive early transition metals acting as electron acceptors and electronegative late transition metals acting as electron donors. We show in this work, through the preparation and systematic study of a series of Mo2M(dpa)4(OTf)2 (M = Cr, Mn, Fe, Co, and Ni; dpa = 2,2'-dipyridylamide; OTf = trifluoromethanesulfonate) heterometallic extended metal atom chain (HEMAC) complexes that this expected trend in χ can be reversed. Physical characterization via single-crystal X-ray diffraction, magnetometry, and spectroscopic methods as well as electronic structure calculations supports the presence of a σ symmetry 3c/3e- bond that is delocalized across the entire metal-atom chain and forms the basis of the heterometallic Mo2-M interaction. The delocalized 3c/3e- interaction is discussed within the context of the analogous 3c/3e- π bonding in the vinoxy radical, CH2CHO. The vinoxy comparison establishes three predictions for the σ symmetry 3c/3e- bond in HEMACS: (1) an umpolung effect that causes the Mo-M interactions to become more covalent as Δχ increases, (2) distortion of the σ bonding and non-bonding orbitals to emphasize Mo-M bonding and de-emphasize Mo-Mo bonding, and (3) an increase in Mo spin population with increasing Mo-M covalency. In agreement with these predictions, we find that the Mo2···M covalency increases with increasing Δχ of the Mo and M atoms (ΔχMo-M increases as M = Cr < Mn < Fe < Co < Ni), an umpolung of the trend predicted in the absence of σ delocalization. We attribute the observed trend in covalency to the decreased energic differential (ΔE) between the heterometal dz2 orbital and the σ bonding molecular orbital of the Mo2 quadruple bond, which serves as an energetically stable, "ligand"-like electron-pair donor to the heterometal ion acceptor. As M is changed from Cr to Ni, the σ bonding and nonbonding orbitals do indeed distort as anticipated, and the spin population of the outer Mo group is increased by at least a factor of 2. These findings provide a predictive framework for multimetallic compounds and advance the current understanding of the electronic structures of molecular heteromultimetallic systems, which can be extrapolated to applications in the context of mixed-metal surface catalysis and multimetallic proteins.

Dataset Information

Heterometallic Molecular Complexes Act as Messenger Building Units to Encode Desired Metal-Atom Combinations to Multivariate Metal-Organic Frameworks.

Publications

Heterometallic Molecular Complexes Act as Messenger Building Units to Encode Desired Metal-Atom Combinations to Multivariate Metal-Organic Frameworks.

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